EP2421916A1 - Procédé de fabrication de mélanges polymères thermoplastiques - Google Patents

Procédé de fabrication de mélanges polymères thermoplastiques

Info

Publication number
EP2421916A1
EP2421916A1 EP10718916A EP10718916A EP2421916A1 EP 2421916 A1 EP2421916 A1 EP 2421916A1 EP 10718916 A EP10718916 A EP 10718916A EP 10718916 A EP10718916 A EP 10718916A EP 2421916 A1 EP2421916 A1 EP 2421916A1
Authority
EP
European Patent Office
Prior art keywords
irradiation
thermoplastic
polymer
energy electrons
kgy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP10718916A
Other languages
German (de)
English (en)
Other versions
EP2421916B1 (fr
Inventor
Kinsuk Naskar
Uwe Gohs
Sven WIEßNER
Andreas Leuteritz
Udo Wagenknecht
Dieter Lehmann
Gert Heinrich
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Leibniz Institut fuer Polymerforschung Dresden eV
Original Assignee
Leibniz Institut fuer Polymerforschung Dresden eV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Leibniz Institut fuer Polymerforschung Dresden eV filed Critical Leibniz Institut fuer Polymerforschung Dresden eV
Publication of EP2421916A1 publication Critical patent/EP2421916A1/fr
Application granted granted Critical
Publication of EP2421916B1 publication Critical patent/EP2421916B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/06—Crosslinking by radiation

Definitions

  • the invention relates to the fields of chemistry and process engineering and relates to a process for the preparation of thermoplastic polymer compounds (eg thermoplastic vulcanizates) from at least two different polymers (eg thermoplastic and elastomer) with optionally polymerizable monomers, filler and reinforcing materials, pigments and additives, which can then be processed into moldings and used, for example, in the automotive industry, in vehicle construction, in the electrical industry.
  • thermoplastic polymer compounds eg thermoplastic vulcanizates
  • at least two different polymers eg thermoplastic and elastomer
  • optionally polymerizable monomers eg polymers, filler and reinforcing materials, pigments and additives
  • Thermoplastic polymer compounds also include thermoplastic vulcanizates (TPV). These consist of a hard and soft phase, the soft phase is more or less cross-linked. The properties of TPVs depend on the proportion, degree of crosslinking, size and dispersion of the particulate soft phase. The elastic properties of the TPV require phase coupling between the hard and soft phases and increase with finer distribution and increasing degree of crosslinking of the elastomer phase. TPVs cover with their material properties a wide field of application of typical rubber applications down to the domain of impact-modified thermoplastics and are particularly suitable for all dynamic and semi-dynamic stressed components. They are z. B.
  • thermoplastic elastomer due to the good skid resistance and with appropriate thermoplastic elastomer combination because of their excellent oil resistance preferably used in automotive applications. Automotive interior applications require TPVs with low fogging and high surface resistivity. These materials are usually based on polypropylene and a finely divided, fully crosslinked elastomer, such. B. polyolefin elastomer.
  • TPVs The current production of TPVs is by means of dynamic vulcanization. That is, during the mixing and dispersing process, the "in situ crosslinking" of the elastomeric phase occurs.
  • dynamic vulcanization was coined in the fundamental work of GESSLER (US 3,037,954 B) and FISCHER (US 3,835,201 B) and from 1977 mainly by the work of CORAN and PATEI (US 4,104,210 B, US 4,130,535 B, US 4,130,535 B
  • the initiation of the crosslinking reaction of the elastomeric phase takes place either by means of thermally activatable free-radical formers, eg peroxides, or thermally activatable polymers (eg phenolic resins) or thermally activatable functional groups (eg B. Reactive amino groups) .Mix process, heat transfer and chemical reaction are interdependent via complex interactions and side reactions, such as the degradation of the thermoplastic matrix, can often not be avoided.
  • TPVs are produced in single-stage processes in continuously operating screw mixing units, eg. B. co-rotating twin-screw extruder, can be produced.
  • screw mixing units eg. B. co-rotating twin-screw extruder
  • Various possibilities of continuous metering of the rubber components have been realized, a known method being rubber extrusion and reactive compounding united (press release of KraussMaffei Berstorff GmbH Hannover, 18.06.2008). This is a particularly interesting solution since the rubber component, which is usually present in non-free-flowing form, can be used directly as a strip without further pretreatment steps
  • the main recipe components eg. As PP and EPDM, plasticized and mixed.
  • additives eg reaction accelerator, filler, UV protection and any dyes
  • dispersing and homogenizing zones as well as other mixing zones for the incorporation of process oils.
  • the addition of the chemical crosslinking agent eg peroxide
  • the TPV is degassed under vacuum before the discharge zone, optionally using a gear pump as discharge, followed.
  • thermoplastic polypropylene PP
  • PE polyethylene
  • PVC polyvinyl chloride
  • PET polyethylene terephthalate
  • PA polyamide
  • EPDM ethylene-propylene-diene rubber
  • NR natural rubber
  • NBR Nitrile rubber
  • MR butyl rubbers
  • XIIR halobutyl rubbers
  • polyethylene so far can not be used, since the limitation of the crosslinking reaction to the soft phase when using thermally activated free-radical generator can hardly be ensured.
  • thermoplastics and elastomers by means of high-energy electrons is state of the art and has hitherto been carried out exclusively under stationary conditions (eg on the molded part, on polymers in the flowable state).
  • Advantages of networking with high-energy electrons are the possibility of manufacturing large components without the use of an autoclave, an increased energy efficiency of up to 70% (compared to the thermal pressing process), low gas emission, shorter curing times, the elimination of additional radical formers and the possibility of complete Incorporation of the materials used into the network (Abaris, EB Curing Technology, Las Vegas, 1994; Norris, R., EB Curing of Composites Workshop, 1996).
  • the object of the present invention is to provide a method for producing thermoplastic polymer compounds with dispersed dispersed crosslinked polymer particles in a simple and cost-effective manner.
  • the object is achieved by the invention specified in the claims.
  • Advantageous embodiments are the subject of the dependent claims.
  • thermoplastic polymer compound materials of at least two different polymers, of which at least one is a thermoplastic and at least one crosslinking polymer, where further substances can be added, are melted in a molten state in time to the dynamic mixing conditions of the production process exposed locally and in terms of intensity irradiation by means of high-energy electrons.
  • a polymer which is an elastomer.
  • two different polymers are used, wherein one polymer is an elastomer and the other polymer is a thermoplastic.
  • a polymer which is an electron-curable reactive resin, wherein advantageously still used as the electron-curable reactive resin is an unsaturated polyester resin or polyester acrylate resin or epoxyacrylates or Urethanacrylatharz or Aminoacrylatharz.
  • the irradiation is carried out by means of high-energy electrons in a reactive gas environment and / or in air.
  • the irradiation is carried out by means of high-energy electrons with dose values in the range from 2 kGy to 250 kGy. It is also advantageous if the irradiation is carried out by means of high-energy electrons with dose rates in the range from 0.1 kGy / U to 500 kGy / U.
  • thermoplastic polymer compounds with dispersed crosslinked polymer particles in which the material morphology, such as the degree of crosslinking, size and dispersion of the crosslinked polymer particles, phase compatibilization and functionalization, are defined locally and in terms of intensity
  • the treatment volume and the gas atmosphere can be controlled defined.
  • the energy input takes place under the dynamic mixing conditions of the manufacturing process, which means in particular the shear and Dehnbe pipe12.
  • the irradiation can also take place before the onset of shear and strain stresses, but according to the invention is only successful if immediately thereafter the shear and strain stresses are realized.
  • the starting materials for producing TPVs are charged with high-energy electrons during the production process.
  • the starting materials used are at least two different polymers, of which at least one is a thermoplastic and at least one is a crosslinking polymer.
  • Crosslinking polymers are to be understood as meaning those which are self-crosslinkable by means of irradiation with high-energy electrons or crosslink using a crosslinking additive.
  • elastomers can be used as crosslinkable polymers in addition to a thermoplastic.
  • thermoplastics it is also possible to use only thermoplastics, it always being necessary to be able to crosslink at least two different thermoplastics by means of irradiation with high-energy electrons.
  • thermoplastics it always being necessary to be able to crosslink at least two different thermoplastics by means of irradiation with high-energy electrons.
  • crosslinking is carried out according to the invention by means of irradiation with high-energy electrons. This can be a radical and / or cationic crosslinking.
  • the irradiation of the starting materials takes place only when the starting materials are in the molten state.
  • excited atoms or molecules as well as ions are generated which preferentially form radicals and induce complex chemical reactions in the treated melt volume of the treatment process.
  • the state of the starting materials is to be understood as molten state, which they usually achieve during the melt processing process according to the prior art, that is, there is no need for any further introduction of temperature in the existing production process.
  • the material morphology is adjusted and controlled according to the invention by the defined controllability of the energy input with regard to the specific location of the polymer melt volume to be modified and also the intensity (intensity, that is, the dose introduced in the modified polymer melt volume per revolution of the compounding machine) of the energy input ,
  • the formation of the desired phase morphology and the physical properties of the TPVs are essentially determined by the screw configuration and the shear and strain stresses introduced into the extrudate. According to the invention, the irradiation takes place promptly to the dynamic mixing conditions of the manufacturing process, whereby the modification according to the invention is effected.
  • the solution according to the invention does not introduce any additional process step into the previous production process for TPVs, but instead exchanges the thermally induced radical formation via additional free-radical formers or thermally activatable polymers (eg phenolic resins) or thermally activatable functional groups by electron-induced radical formation.
  • An advantage of the solution according to the invention is that the polymer radicals can be generated independently of the temperature in a selectable treatment area within the material mass and / or in the manufacturing process according to the requirements of the desired chemical reaction. This means that the chemical reaction can only be triggered in a specifically selected area within the material mass.
  • a local and / or temporal sequential irradiation can be done in a continuous or discontinuous compounding machine for polymer melt, but the molten state of the material must already be present.
  • the irradiation in an extruder at any desired location of the extruder with a corresponding structure of cylinder and screw in the region of the irradiation locations can be carried out, but the molten state of the material must already be present.
  • the irradiation with high-energy electrons in the melt preparation process is realized with a dose (dose, that is to say absorbed energy per unit mass) per revolution adapted to the system to be modified.
  • dose that is to say absorbed energy per unit mass
  • the energy input is chosen depending on the material composition of the melt.
  • thermoplastic matrix it is also possible to realize a control of the material morphology by means of the temporally and spatially precisely controllable energy input by the high-energy electrons.
  • the degree of crosslinking, the size and dispersion of the crosslinked polymer particles, the phase compatibilization and the functionalization of the thermoplastic matrix can be largely controlled by the dose introduced per revolution, the treatment volume and the gas atmosphere.
  • the irradiation can be carried out in a reactive gas environment and / or in air and / or in a vacuum.
  • the particular advantage of the present solution consists not only in the crosslinking of the elastomeric phase but also in the fact that with the energy input by eergergereiche electrons functional groups can be generated, the lead to a better compatibility of the material systems and an increase in the hydrophilicity of the surface.
  • a TPV consisting of a polypropylene homopolymer (50% by mass) and an ethylene-propylene-diene rubber (EPDM; 50% by mass) is prepared by irradiation with electrons in a Brabender kneading chamber under the following conditions:
  • Treatment time 60 absorbed dose [kGy]: 50 absorbed dose per revolution [kGy / U]: ⁇ 11 Gas atmosphere: air
  • the TPV is processed into a test rod (pressing), on which the following properties were determined:
  • a TPV consisting of a polypropylene homopolymer (50% by mass) and an ethylene-propylene-diene rubber (EPDM; 50% by mass) is prepared by irradiation with electrons in a Brabender kneading chamber under the following conditions:
  • Treatment time 60 absorbed dose [kGy]: 100 absorbed dose per revolution [kGy / U]: ⁇ 22 Gas atmosphere: air
  • the TPV is processed into a test rod (pressing), on which the following properties were determined:
  • a TPV consisting of a polypropylene homopolymer (50% by mass) and an ethylene-propylene-diene rubber (EPDM; 50% by mass) is prepared by irradiation with electrons in a Brabender kneading chamber under the following conditions:
  • Treatment time [s] 15 absorbed dose [kGy] 100 absorbed dose per revolution [kGy / U] - 90
  • the TPV is processed into a test rod (pressing), on which the following properties were determined:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne le domaine de la chimie et de la technique des procédés et porte sur un procédé de fabrication de mélanges polymères thermoplastiques (par exemple de vulcanisats thermoplastiques) à partir d'au moins deux polymères différents (par exemple un polymère thermoplastique et un élastomère) avec, le cas échéant des monomères polymérisables, des charges et des agents de renforcement, des pigments ainsi que des additifs, lesquels mélanges polymères thermoplastiques peuvent être transformés en pièces moulées et peuvent être utilisés par exemple dans l'industrie automobile, dans la fabrication de véhicules et dans l'industrie électronique. L'objet de la présente invention est la mise au point d'un procédé de fabrication de mélanges polymères thermoplastiques avec des particules polymères réticulées réparties de façon dispersée, d'une manière simple et économique. A cet effet, selon ledit procédé de fabrication d'un mélange polymère thermoplastique, des matières constituées d'au moins deux polymères différents, dont au moins un est un polymère thermoplastique et au moins un est un polymère réticulant, sont exposées, dans un état fluide fondu proche dans le temps des conditions de mélange dynamique du processus de fabrication, à un rayonnement, défini localement et en ce qui concerne l'intensité, d'électrons à grande énergie.
EP10718916.9A 2009-04-24 2010-04-16 Procédé de fabrication des composés polymères thermoplastiques Not-in-force EP2421916B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009002642A DE102009002642A1 (de) 2009-04-24 2009-04-24 Verfahren zur Herstellung thermoplastischer Polymercompounds
PCT/EP2010/055022 WO2010121960A1 (fr) 2009-04-24 2010-04-16 Procédé de fabrication de mélanges polymères thermoplastiques

Publications (2)

Publication Number Publication Date
EP2421916A1 true EP2421916A1 (fr) 2012-02-29
EP2421916B1 EP2421916B1 (fr) 2013-11-06

Family

ID=42316040

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10718916.9A Not-in-force EP2421916B1 (fr) 2009-04-24 2010-04-16 Procédé de fabrication des composés polymères thermoplastiques

Country Status (4)

Country Link
EP (1) EP2421916B1 (fr)
DE (1) DE102009002642A1 (fr)
DK (1) DK2421916T3 (fr)
WO (1) WO2010121960A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3051538A1 (fr) 2015-01-27 2016-08-03 Lapp Engineering & Co. Procédé de production d'un matériau isolant

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103589307A (zh) * 2013-11-14 2014-02-19 惠州市长润发涂料有限公司 一种高填充uv透明底漆

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US3037954A (en) 1958-12-15 1962-06-05 Exxon Research Engineering Co Process for preparing a vulcanized blend of crystalline polypropylene and chlorinated butyl rubber
US3098806A (en) * 1959-12-10 1963-07-23 Gen Mills Inc Cross linking of fatty polyamides with ionizing radiation
DD112588A3 (fr) * 1970-02-20 1975-04-20
GB1348911A (en) * 1971-02-05 1974-03-27 Schwarza Chemiefaser Process for the production of synthetic filaments and planar bodies
US3835201A (en) 1972-08-29 1974-09-10 Uniroyal Inc Thermoplastic blend of copolymer rubber and polyolefin plastic
US4130535A (en) 1975-07-21 1978-12-19 Monsanto Company Thermoplastic vulcanizates of olefin rubber and polyolefin resin
US4104210A (en) 1975-12-17 1978-08-01 Monsanto Company Thermoplastic compositions of high unsaturation diene rubber and polyolefin resin
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US7521508B2 (en) * 2004-06-30 2009-04-21 Freudenberg-Nok General Partnership Electron beam inter-curing of plastic and elastomer blends
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3051538A1 (fr) 2015-01-27 2016-08-03 Lapp Engineering & Co. Procédé de production d'un matériau isolant

Also Published As

Publication number Publication date
DE102009002642A1 (de) 2010-10-28
DK2421916T3 (da) 2014-02-10
EP2421916B1 (fr) 2013-11-06
WO2010121960A1 (fr) 2010-10-28
DE102009002642A8 (de) 2011-06-01

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